EP2106414B1 - Thermoplastische elastomere aus styrol-blockcopolymeren und aliphatischen thermoplastischen polyurethanen - Google Patents

Thermoplastische elastomere aus styrol-blockcopolymeren und aliphatischen thermoplastischen polyurethanen Download PDF

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Publication number
EP2106414B1
EP2106414B1 EP07843528.6A EP07843528A EP2106414B1 EP 2106414 B1 EP2106414 B1 EP 2106414B1 EP 07843528 A EP07843528 A EP 07843528A EP 2106414 B1 EP2106414 B1 EP 2106414B1
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compound
styrene
article
component
agents
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French (fr)
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EP2106414A2 (de
EP2106414A4 (de
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Charles Page
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Avient Corp
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Polyone Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • This invention relates to thermoplastic elastomers, polymer compounds which exhibit elasticity while remaining thermoplastic.
  • thermoplastic elastomers combine the benefits of elastomeric performance properties of thermoset polymers, such as vulcanized rubber, with the processing properties of thermoplastic polymers.
  • multiple component extrusion or molding has recently become popular to provide one type of rheology in one part of the component and a second type of rheology in a second part of the component.
  • a specific use of multiple component thermoplastic compounds is insulating strips for vehicle doors.
  • One part has a relatively rigid rheological structure for securing the component to the door, with the second part being a relative flexible rheological structure to compress and seal the door to the vehicle.
  • TPEs modified for adhesion to polar substrates, for use in these multi-component molding applications are well established, and methods to improve adhesion and well known in the industry.
  • One such method for improving the adhesion of normally apolar TPEs is disclosed in US Pat. No. 5,472,782 .
  • One problem with these common methods is the resulting compound is always opaque, due to the immiscibility and difference in refractive index of the modifiers employed.
  • Thermoplastic polyurethanes are linear polymers formed by the polymerization reaction of a diisocyanate, a short chain diol as a chain extender, and a long chain diol or polyol.
  • the diisocyanate groups form the hard segment of the TPE and are rigid at room temperature.
  • the molecules are attracted to one another forming crystallites which act as reversible, physical cross-links.
  • the long chain diol and the diisocyanate react to form soft segments that are flexible at room temperature and bring about the rubbery nature of the TPU.
  • Typical diisocyanates used in the production of TPUs are toluene di-isocyanate (TDI) and diphenyl methane di-isocyanate (MDI), both of these diisocyanates being aromatic and therefore imparting some less desirable properties upon the TPU, such as poor UV and hydrolysis resistance.
  • TDI toluene di-isocyanate
  • MDI diphenyl methane di-isocyanate
  • Newly introduced aliphatic diisocyanates while expensive, overcome these problems of aromatic-based diisocyanates, and furthermore have a lower refractive index than such aromatic-based diisocyanates.
  • JP 2005 187721 A relates to the problem of transparency of thermoplastic elastomer compositions.
  • the examples 1-4 of JP 2005 187721 A describe compositions comprising a styrene-isobutylene-styrene block copolymer and an ester-based TPU.
  • thermoplastic elastomer also called "TPE”
  • TPE thermoplastic elastomer
  • the present invention solves the problem in the art by using aliphatic polycaprolactone TPUs made from aliphatic diisocyanates as a modifying additive for a TPE using a styrenic block copolymer, such as styrene-ethylene-butylene-styrene (SEBS) as the thermoplastic matrix for the compound.
  • SEBS styrene-ethylene-butylene-styrene
  • the invention benefits from the use of TPUs made from aliphatic diisocyanates (“aliphatic TPU") because the refractive index of the aliphatic TPU is similar to or compatible with the refractive index of the SEBS.
  • the second component of the multiple component part can also be translucent or nearly transparent in visible spectrum light.
  • the second component compound is often selected from such engineering thermoplastics as polyamides (PAs), polycarbonates (PCs), acrylonitrile/butylene/styrene (ABS) and blends of PC and ABS.
  • Other compounds suitable for the second component include acrylic resins (including polymethylmethacrylate (PMMA), acrylate-styrene-acrylate (ASA) and methylmethacrylate ABS (MABS)), polyesters and their blends (polybutylene terephthalate, polyethylene terephthalate, and their blends with polycarbonate), and polyoxymethylene, also known as acetal.
  • the first component benefiting from the present invention has excellent adhesion to these engineering thermoplastic compounds.
  • one aspect of the present invention is a multiple component extruded or molded part exhibiting at least translucency, wherein the first component comprises a blend of a styrenic block copolymer and aliphatic polycaprolactone TPU and wherein the second component comprises an engineering thermoplastic selected from the group consisting of polyamides (PAs), polycarbonates (PCs), acrylonitrile/butylene/styrene (ABS) and blends thereof.
  • PAs polyamides
  • PCs polycarbonates
  • ABS acrylonitrile/butylene/styrene
  • the styrenic block copolymer that has thermoplastic elastomer properties is selected from styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-ethylene/propylene-styrene, styrene-isobutylene-styrene, styrene-butadiene-styrene, styrene-isoprene-styrene, and combinations thereof.
  • TPE-S are not maleated but have weight average molecular weights in excess of 100,000 and preferably in excess of 200,000.
  • Commercially available grades of these TPE-S compounds are Kraton G1651 and Kraton MD 6917 from Kraton Polymers and Septon 8006 from Kuraray.
  • Any compound that is compatible with the selected TPE-S compounds is eligible to serve as a compatibilizer between the TPE-S and the aliphatic polycaprolactone TPU.
  • compatibilizers include Septon TU-S 5265 TPU-SBC copolymer from Kuraray.
  • Any aliphatic polycaprolactone thermoplastic polyurethane that is made from one or more aliphatic diisocyanates is eligible for use in the present invention.
  • a non-limiting example of commercially available aliphatic polycaprolactone TPU includes Pearlthane D91T85 aliphatic polycaprolactone TPU available from Merquinsa Mercados Quimicos S.L. of Barcelona, Spain.
  • the compound of the present invention can include conventional plastics additives in an amount that is sufficient to obtain a desired processing or performance property for the compound.
  • the amount should not be wasteful of the additive nor detrimental to the processing or performance of the compound.
  • Those skilled in the art of thermoplastics compounding without undue experimentation but with reference to such treatises as Plastics Additives Database (2004) from Plastics Design Library (www.williamandrew.com), can select from many different types of additives for inclusion into the compounds of the present invention.
  • Non-limiting examples of optional additives include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppresants; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes; plasticizers; processing aids; release agents; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; and combinations of them.
  • adhesion promoters include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppresants; impact modifiers;
  • a paraffinic oil is used as a plasticizer to adjust rheology of the TPE.
  • Table 1 shows the acceptable, desirable, and preferable ranges of ingredients for the TPE of the present invention.
  • Table 1 Ranges of Ingredients Ingredient (Wt. Percent) Acceptable Desirable Preferable TPE matrix (styrenic block copolymer) 5 - 65% 10 - 35% 18 - 22% Compatibilizer 0 - 30% 5 - 20% 10 - 15% Plasticizer oil 0 - 35% 10 - 30% 15 - 30% Modifier resin (aliphatic TPU) 10 - 95% 30 - 60% 40 - 50% Antioxidant 0 - 1.0% 0.05 - 0.5% 0.05 - 0.15% Hindered Amine Light Stabilizer 0 - 1.0% 0.1 - 0.5% 0.25 - 0.45% UV absorber 0 - 1.0% 0.1 - 1.0% 0.2 - 0.4% Mold Release Agent 0 - 0.5% 0.05 - 0.3% 0.05 - 0.15% Other optional additives 0 - 10% 0 - 10% - 10% - 10% - 10% - 10%
  • the preparation of compounds of the present invention is uncomplicated.
  • the compound of the present can be made in batch or continuous operations.
  • Extruder speeds can range from about 50 to about 500 revolutions per minute (rpm), and preferably from about 100 to about 300 rpm.
  • the output from the extruder is pelletized for later extrusion or molding into polymeric articles.
  • Mixing in a batch process typically occurs in a Banbury mixer that is also elevated to a temperature that is sufficient to melt the polymer matrix to permit homogenization of the compound components.
  • the mixing speeds range from 60 to 1000 rpm and temperature of mixing can be ambient. Also, the output from the mixer is chopped into smaller sizes for later extrusion or molding into polymeric articles.
  • the TPE-S/Aliphatic TPU blend of the present invention is an excellent one part of a multiple component polymer structure because it has excellent adhesion to engineering thermoplastic compounds identified above.
  • Table 2 shows the commercial sources for the ingredients of Table 1 and also used as ingredients for the Examples.
  • Table 3 shows the formulations of Examples 1 and 2 and of Reference Example 3 and Comparative Example A.
  • Table 2 Source of Ingredients Ingredient Name Purpose Generic Name Commercial Source Source Location Kraton G 1650 TPE matrix SEBS Kraton France Kraton MD 6917 ES TPE Matrix SEBS Kraton France TU-S 5265 Compatibilizer TPU-SBC copolymer Kuraray Japan Primol 382 Plasticizer Paraffinic White Oil ExxonMobil Europe Pearlthane D91T85 Modifier resin Aliphatic, polycaprolactone TPU Merquinsa Spain Pearlthane 11T85 Modifier Resin Aromatic, polycaprolactone TPU Merquinsa Spain Pearlcoat D191K Modifier Resin Aliphatic, ether TPU Merquinsa Spain Irganox 1010 Antioxidant Pentaerythritol Tetrakis CAS:6683-19-8 Ciba Europe Chi
  • a Kraton G 1650 20 - - - Kraton MD 6917 - 21 21 21 TU-S 5265 15 12 12 12 Primol 382 17 25 25 25 Pearlthane D91 T85 48 42 - - Pearlcoat D191K - - 42 - Pearlthane 11T85 - - - 42 Irganox 1010 0.11 0.11 0.11 0.11 Chimassorb 944 0.38 - - - Tinuvin P 0.3 - - - Tinuvin 327 - 0.26 0.26 0.26 Erucamide - 0.1 0.1 0.1 Mixing Equipment W&P ZE25 twin screw compounder Mixing Temp. (°C) Increasing in temperature from throat to die 180-200 180-200 180-200 200-240 Mixing Speed 320rpm Order of Addition of Ingredients All added at Zone 1 except for 10% oil added at the injection port Form of Product After Mixing Pellets
  • Pellets of all Examples 1-3 and Comparative Example A were molded into tensile test bars using a Demag injection molding machine, operating at 180-200°C temperature and medium-high pressure.
  • the following test method was used. Using the Demag injection molding machine with dual barrels, PA or PC or ABS was injected first into a custom designed tool with a moving core, after which the TPE compound was injected directly onto the PA or PC or ABS.
  • the two-component (“2K") test bars were ejected and conditioned at room temperature for 24 hours. After conditioning, an attempt was made by hand to remove the TPE strip from the engineering polymer substrate, and the difficulty noted. Additionally it was noted whether the bond failed by adhesive failure (where the TPE is cleanly removed from the substrate) or by cohesive failure (where a layer of TPE remains on the substrate, the interfacial strength is higher than the cohesive strength of the TPE, the optimal case).
  • Table 4 shows the experimental results. Table 4 Experimental Results Example 1 2 3 (Ref.) Comp. A Shore Durometer (DIN 53 505) 68 A 60 60 60 Density (DIN 53479-A) 1.008 g/cm 3 0.985 g/cm 3 0.957 g/cm 3 1.008 g/cm 3 MFI (190C/5Kg) DIN EN ISO 815 220 g/10min 10.5 g/10min 15 g/10min 2 g/10min Tensile Strength (DIN 53504) 9.5 MPa 5.6 MPa 4.4 MPa 9.0 MPa Elongation at Break (DIN 53504) 520% 615% 475% 520% Transparency (visual/ subjective) Good Good Translucent Opaque Adhesion to PA6 Excellent (cohesive Excellent (cohesive Poor (adhesive Excellent (cohesive (subjective) failure) failure) failure) failure) Adhesion to PC (subjective) Excellent (cohesive failure) Excellent (cohesive failure)

Claims (13)

  1. Thermoplastisches Elastomer-Compound, umfassend:
    (a) Styrol-Blockcopolymer, ausgewählt aus der Gruppe bestehend aus Styrol-Ethylen-Butylen-Styrol, Styrol-Ethylen-Propylen-Styrol, Styrol-Ethylen-Ethylen/Propylen-Styrol, Styrol-Isobutylen-Styrol, Styrol-Butadien-Styrol, Styrol-Isopren-Styrol und Kombinationen davon, und
    (b) aliphatisches thermoplastisches Polycaprolacton-Polyurethan.
  2. Compound nach Anspruch 1, wobei das Styrol-Blockcopolymer eine gewichtsmittlere Molmasse von über 100.000 hat.
  3. Compound nach Anspruch 1 oder Anspruch 2, wobei das Compound weiterhin einen Zuschlagsstoff umfasst, der ausgewählt ist aus der Gruppe bestehend aus Haftvermittlern; Bioziden; Antibeschlagmitteln; Antistatika; Treibmitteln; Bindemitteln; Schäummitteln; Dispergiermitteln; Füllstoffen; Streckmitteln; Feuerschutzmitteln; Flammschutzmitteln; rauchunterdrückenden Mitteln; Schlagzähmodifikatoren; Initiatoren; Schmiermitteln; Glimmer; Pigmenten; Farbmitteln; Farbstoffen; Weichmachern; Verarbeitungshilfen; Trennmitteln; Silanen, Titanaten; Zirkonaten; Gleitmitteln; Antiblockmitteln; Stabilisatoren; Stearaten; UV-Absorbern; Viskositätsregulatoren; Wachsen; und Kombinationen davon.
  4. Compound nach Anspruch 3, wobei der Weichmacher ein Paraffinöl ist.
  5. Compound nach einem der vorhergehenden Ansprüche, wobei die Menge an Styrol-Blockcopolymer 5 bis 65 Gewichtsprozent des Compounds ausmacht, und wobei die Menge an aliphatischem thermoplastischen Polyurethan 10 bis 95 Gewichtsprozent des Compounds ausmacht.
  6. Compound nach einem der vorhergehenden Ansprüche, wobei die Menge an Styrol-Blockcopolymer 10 bis 35 Gewichtsprozent des Compounds ausmacht, und wobei die Menge an aliphatischem thermoplastischen Polyurethan 30 bis 60 Gewichtsprozent des Compounds ausmacht.
  7. Compound nach einem der vorhergehenden Ansprüche, wobei die Menge an Styrol-Blockcopolymer 18 bis 22 Gewichtsprozent des Compounds ausmacht, und wobei die Menge an aliphatischem thermoplastischen Polyurethan 40 bis 50 Gewichtsprozent des Compounds ausmacht.
  8. Mehrkomponentenartikel, umfassend das Compound nach einem der Ansprüche 1-7 als erste Komponente und ein technisches thermoplastisches Compound als eine zweite Komponente.
  9. Artikel nach Anspruch 8, wobei der Artikel geformt ist und die zweite Komponente ausgewählt ist aus der Gruppe bestehend aus Polyamiden, Polycarbonaten, Acrylnitril/Butylen/Styrol, Acrylharzderivaten, Polyestern und ihren Mischungen und Polyoxymethylen, und Mischungen davon.
  10. Artikel nach Anspruch 8, wobei der Artikel extrudiert ist und die zweite Komponente ausgewählt ist aus der Gruppe bestehend aus Polyamiden, Polycarbonaten, Acrylnitril/Butylen/Styrol, Acrylharzderivaten, Polyestern und ihren Mischungen und Polyoxymethylen, und Mischungen davon.
  11. Artikel nach einem der Ansprüche 8-10, wobei der Artikel als Fahrzeugtürdichtung ausgebildet ist.
  12. Artikel nach einem der Ansprüche 8-10, wobei der Artikel als ein Teil ausgebildet ist, das ausgewählt ist aus der Gruppe bestehend aus einem Elektrowerkzeuggriff, einer integrierten Dichtung, einem integrierten Dichtungsring, einem Hydrolager, einem Stück einer Autoinnenverkleidung, einem schalldämpfenden Teil, einer Verglasungsdichtung und einer flexiblen Membran.
  13. Artikel nach einem der Ansprüche 8-12, wobei die erste Komponente an der zweiten Komponente haftet und wobei ein Adhäsionsbruch bei Anlegen einer Trennkraft zu einem Kohäsionsbruch führt, wobei nach Anlegen der Trennkraft eine Schicht der ersten Komponente an der zweiten Komponente verbleibt.
EP07843528.6A 2006-10-05 2007-09-28 Thermoplastische elastomere aus styrol-blockcopolymeren und aliphatischen thermoplastischen polyurethanen Active EP2106414B1 (de)

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US82836206P 2006-10-05 2006-10-05
PCT/US2007/079960 WO2008045702A2 (en) 2006-10-05 2007-09-28 Thermoplastic elastomers of styrenic block copolymers and aliphatic thermoplastic polyurethanes

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EP2106414A2 EP2106414A2 (de) 2009-10-07
EP2106414A4 EP2106414A4 (de) 2012-07-25
EP2106414B1 true EP2106414B1 (de) 2014-08-20

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WO2020146301A1 (en) * 2019-01-09 2020-07-16 Polyone Corporation Thermoplastic polyurethane compounds exhibiting enhanced stain resistance
WO2020146323A1 (en) * 2019-01-09 2020-07-16 Polyone Corporation Thermoplastic polyurethane compounds exhibiting enhanced stain resistance
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WO2020146301A1 (en) * 2019-01-09 2020-07-16 Polyone Corporation Thermoplastic polyurethane compounds exhibiting enhanced stain resistance
WO2020146323A1 (en) * 2019-01-09 2020-07-16 Polyone Corporation Thermoplastic polyurethane compounds exhibiting enhanced stain resistance
CN110105745A (zh) * 2019-05-23 2019-08-09 厦门扬丰塑胶科技有限公司 一种塑料制品橡胶材料及其制备方法

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EP2106414A2 (de) 2009-10-07
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WO2008045702A2 (en) 2008-04-17
US20100160545A1 (en) 2010-06-24

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